Catalyst system for selective hydrogenation of heteroaromatic sulfur-containing and nitrogen-containing compounds, and process for preparing and using same

ABSTRACT

A catalyst system for selective hydrogenation of sulfur-containing and nitrogen-containing compounds of a heteroaromatic organic phase includes a mixture of a noble metal selected from Group VIII of the Periodic Table of Elements and a water-soluble ligand. A process for preparing the catalyst system and hydrogenation process using the catalyst system are also provided.

This is a Division, of application Ser. No. 08/657,960, filed Jun. 4,1996, now U.S. Pat. No. 5,753,584.

BACKGROUND OF THE INVENTION

The invention relates to a catalyst system, a process for preparing thecatalyst system, and a process for hydrogenating heteroaromaticcompounds containing nitrogen and sulfur using a catalyst system.

The removal of sulfur and nitrogen contaminants from petroleumderivatives, especially without a reduction of octane number, is ofcritical importance in the oil industry. Although numerous methods andcatalysts have been disclosed for use in removing sulfur and nitrogen,the need remains for a catalyst system which is useful for selectivehydrogenation of aromatic compounds containing sulfur and nitrogen inorder to convert refractive aromatic compounds into labile aromaticcompounds.

It is therefore the primary object of the present invention to provide acatalyst system which is selective to hydrogenation of aromaticcompounds containing sulfur and nitrogen.

It is a further object of the present invention to provide a catalystsystem for selective hydrogenation of sulfur and nitrogen compounds,which catalyst system is water-soluble.

It is a further object of the present invention to provide a catalystsystem which can be formed in situ at the site of reaction orhydrogenation.

It is another object of the present invention to provide a process forpreparing a catalyst system in accordance with the invention.

It is still another object of the present invention to provide a processfor selective hydrogenation of aromatic compounds containing sulfur andnitrogen using a catalyst system according to the present invention.

Other objects and advantages of the present invention will appearhereinbelow.

SUMMARY OF THE INVENTION

In accordance with the present invention, the foregoing objects andadvantages are readily attained.

According to the invention, a catalyst system is provided for selectivehydrogenation of sulfur-containing and nitrogen-containing compounds ofa heteroaromatic organic phase, wherein the catalyst system comprises amixture of a noble metal selected from group VIII of the Periodic Tableof Element and a water-soluble ligand. In further accordance with theinvention, an organic nitrogen base may be included in the catalystsystem so as to speed the hydrogenation reaction in the presence of thecatalyst system of the present invention as will be further discussedbelow.

The noble metal is preferably selected from the group consisting ofruthenium, rhodium, palladium, iridium and mixtures thereof.

The water-soluble ligand is preferably a sulfonated aryl phosphine suchas m-mono sulfonated triphenyl phosphine, tri (m-sulfonated) triphenylphosphine and mixtures thereof, or biquinoline such as2,2'-biquinoline-4,4'-dicarboxylic acid in dipotassium salt form,trihydrate; 2,2'-biquinoline-5,5'-disulfonated in disodium salt form,dihydrate and mixtures thereof.

In further accordance with the present invention, a process forpreparing a catalyst system for selective hydrogenation ofsulfur-containing and nitrogen-containing compounds of a heteroaromaticorganic phase is provided which process comprises the step of forming amixture of a noble metal selected from Group VIII of the Periodic Tableof Elements and a water-soluble ligand in water so as to provide anaqueous catalyst system.

Still further according to the invention, a process for selectivehydrogenation of sulfur-containing and nitrogen-containing compoundsfrom a heteroaromatic organic phase is provided, which process comprisesreacting the organic phase with hydrogen in the presence of a catalystsystem comprising a mixture of a noble metal selected from group VIII ofthe Periodic Table of Elements and a water-soluble ligand at reactionconditions so as to selectively hydrogenate sulfur-containing andnitrogen-containing compounds from the organic phase.

DETAILED DESCRIPTION

The present invention relates to a catalyst system for selectivehydrogenation of sulfur-containing and nitrogen-containing compounds ofa heteroaromatic organic phase. The catalyst system of the presentinvention is a water-soluble mixture of a noble metal selected fromGroup VIII of the Periodic Table of Elements and a water-soluble ligand.

In accordance with the invention, the water-soluble catalyst system maybe dissolved into an aqueous solution which solution is mixed with anorganic phase containing the sulfur-containing and nitrogen-containingcompounds to be hydrogenated, and the reaction mixture so obtained isthen exposed to hydrogen under hydrogenation conditions so as toselectively hydrogenate the sulfur and nitrogen compounds withoutsignificantly adversely affecting the octane number of the organicphase.

The noble metal of the catalyst system of the present invention ispreferably selected from the group consisting of ruthenium, rhodium,palladium, iridium, platinum and mixtures thereof. The noble metal foruse in the catalyst system of the present invention may preferably beprovided in the form of a water-soluble salt, most preferably achloride, bromide or iodide salt, and may alternatively be provided as awater-soluble organometallic compound as will be further discussedbelow.

The water-soluble ligand of the present invention may suitably be asulfonated aryl phosphine such as m-monotrisulfonated triphenylphosphine (TPPMS), most preferably in the sodium salt form, or tri(m-sulfonated) triphenyl phosphine (TPPTS). TPPMS may suitably beprepared in accordance with the procedure published by S. Ahrland, J.Chatt, N. Davies and A. Williams in J. Chem. Soc. (1958), page 276.TPPTS may suitably be prepared according to the invention by followingthe procedure described in French Patent No. 2,314,910, or as improvedby the procedure described by T. Bartik, B. Bartic, B. E. Hanson, T.Glass, and W. Bebout in Inorg. Chem., Volume 31 (1992), pages 2667-2670.Alternatively, the water-soluble ligand of the present invention maysuitably be a biquinoline water-soluble ligand such as2,2'-biquinoline-4,4'-dicarboxylic acid, dipotassium salt trihydrate,which is available from Aldrich Chemical Co., or2,2'-biquinoline-5,5'-disulfonated, disodium salt which may be preparedby controlled sulfonation of 2,2'-biquinoline with sulfuric acid and 30%SO₃ and following the details described by S. Anderson, E. C. Constable,K. R. Seddon, J. E. Turp, J. E. Barggott and M. J. Pilling in J. Chem.Soc., Dalton Trans., (1985) 2247-2261.

In further accordance with the invention, the catalyst system may beprovided with noble metal and at least a portion of the water-solubleligand by providing the noble metal as an organometallic compound suchas metal-trisacetylacetonate, metal-bisacetylacetonate and mixturethereof, which compounds include water-soluble ligand. This isadvantageous in that the preparation of the catalyst system according tothe invention can be simplified by performing the addition of a singleingredient to water, if desired.

In further accordance with the invention, an organic nitrogen base maybe included in the catalyst system so as to speed the hydrogenationreaction in the presence of the catalyst system of the present inventionas will be further discussed below. According to the invention, theorganic nitrogen base may suitably be selected from the group consistingof aniline, quinoline, isoquinoline, tetrahydroquinoline,decahydroquinoline, acridine, piperidine, triethylamine and mixturesthereof. As will be set forth below, the organic nitrogen base serves tospeed the hydrogenation reaction, although in some cases thisacceleration of the process is not necessary. Thus, in accordance withthe present invention, the organic nitrogen base may be desirable usedas a co-catalyst additive to the catalyst system of the presentinvention.

In further accordance with the invention, it has been found preferableto provide noble metal and water-soluble ligand in the catalyst systemof the present invention in a molar ratio of metal, measured as a salt,to water-soluble ligand of between about 1:1 to about 1:10 and morepreferably between about 1:3 to about 1:6. Further, when an organicnitrogen base is to be used, it has been found advantageous to maintaina molar ratio of metal to organic nitrogen base of between about 1:1 toabout 1:20, more preferably between about 1:2 to about 1:6, and furtherto provide and maintain a molar ratio of water-soluble ligand to organicnitrogen base of between about 1:1 to about 1:6, more preferable betweenabout 1:2 to about 1:4.

As will be set forth below, the catalyst system of the present inventionexhibits excellent selectivity toward the hydrogenation reaction ofsulfur and nitrogen-containing compounds of heteroaromatic organic phasewithout reducing normal aromatic compounds such as benzene, toluene,naphthalene and the like.

The catalyst system of the present invention is designed to be used in abi-phase system formed between two immiscible liquids. One liquid phaseis water, in which the water-soluble catalyst system of the presentinvention is dissolved. The other liquid phase is an organic phase suchas a hydrocarbon containing the unwanted sulfur and nitrogencontaminants which are to be hydrogenated in accordance with the presentinvention.

The catalyst system of the present invention may preferably be preparedin accordance with several methods. Each of these methods will bediscussed below. It should of course be noted, however, that numerousalternative methods for preparing the catalyst system of the presentinvention could be provided.

In accordance with one embodiment of the invention, the source of noblemetal, water-soluble ligand and nitrogen base may be added directly tothe desired volume of water, preferably adding each component one at atime while the water solution is subjected to continuous stirring.

In accordance with an alternative embodiment, the catalyst system of thepresent invention may be prepared by dividing the desired amount ofwater into separate volumes, preferably separate equal volumes, andpreparing two aqueous solutions. The first aqueous solution is preparedusing the source of noble metal, while the second aqueous solution isprepared using the water-soluble ligand. The metal aqueous solution isthen added to the ligand aqueous solution, again during continuousstirring. In accordance with this embodiment, the organic nitrogen baseis preferably added after the first solution is completely added to thesecond solution.

In accordance with another embodiment of the present invention, thecatalyst system may suitably be prepared similar to that describedabove, with the exception that the ligand aqueous solution is added tothe metal aqueous solution. This method of preparation has been found toprovide excellent conversion of nitrogen and sulfur contaminants as willbe demonstrated below.

The different characteristics provided to the catalyst system of thepresent invention by each of the above preparation methods will befurther illustrated in the examples set forth below.

After formation of the catalyst system of the present invention it ispreferable, and enhanced hydrogenation activity is provided, if thecatalyst system is activated so as to form active species within thecatalyst system as desired. The catalyst system of the present inventionmay suitably be activated by forming the aqueous solution containing thecatalyst system by one of the methods discussed above, and exposing theaqueous catalyst system to hydrogen at hydrogenation pressure andtemperature, preferably between about 40° C. to about 140° C. and 100psi to about 1500 psi.

In accordance with the invention, the aqueous catalyst system of thepresent invention may suitably be activated individually, prior tomixture with the organic phase to be treated, or alternatively theaqueous catalyst system of the present invention may be introducedsubstantially simultaneously into the reactor with the organic phasecontaining the aromatic sulfur and nitrogen to be reduced. When theaqueous catalyst system is introduced simultaneously with the organicphase, the bi-phase system is again subjected to hydrogenationconditions as set forth above, as well as stirring, preferably avigorous stirring, so as to provide active species on the catalystsystem as desired.

In accordance with the invention, the stirring has been found to be animportant part of the catalyst system activation, and the more vigorousthe stirring, the more efficient hydrogenation will be provided.Stirring is preferably conducted at a rate of between about 500 rpm toabout 5000 rpm.

As set forth above, the catalyst system of the present invention is wellsuited for the selective hydrogenation of sulfur and nitrogen-containingcompounds of a particular organic phase. The catalyst system is selectedfor the hydrogenation of aromatic compounds containing sulfur andnitrogen only. The catalyst system does not induce reduction ofcarbon-hydrogen aromatic compounds of a heteroaromatic organic phase.Further, the catalyst system does not enhance reduction of normal anddesirable aromatic compounds such as benzene, toluene, naphthalene andthe like. Thus, the catalyst system of the present invention isparticularly well suited to use in hydrogenation reactions for organicphases such as any straight non-hydrogenated hydrocarbon such asdecalin, hexane, n-decane, cyclohexane, and the like, or any FCC naphthaor other petroleum derivative. The catalyst system of the presentinvention is useful in hydrogenation of aromatic sulfur andnitrogen-containing compounds such as thiophenes, benzothiophenes andquinolines.

In use, the catalyst system of the present invention is provided in anaqueous solution as discussed above, and mixed with an organic phase ata ratio of aqueous phase:organic phase in the range of between about90:10 to about 10:90. The mixture of aqueous catalyst system and organicphase preferably further includes a molar ratio of sulfur-nitrogencompounds:catalyst system of between about 100:1 to about 5:1, a metalsalt:water-soluble ligand molar ratio of between about 1:20 to about1:1, and a metal salt:nitrogen base molar ratio of between about 1:10 toabout 1:1.

The mixture of aqueous catalyst system and organic phase is preferablyprepared in situ in accordance with the present invention by mixing thetwo immiscible phases on site in the reactor. As set forth above, theaqueous catalyst system is preferably activated, either prior to orduring the introduction of organic phase. After suitable activation, thehydrogenation reaction is then carried out. During this reaction, thebi-phase aqueous catalyst system and organic phase mixture is exposed tohydrogen under hydrogenation conditions, preferably including atemperature between about 40° C. to about 140° C. and a pressure ofbetween about 100 psi to about 1500 psi, so as to hydrogenate theorganic phase, and thereby convert undesirable sulfur and nitrogenaromatic compounds as desired.

The catalyst system of the present invention can be used in thehydrogenation process described above according to the invention so asto treat organic phase containing aromatic sulfur in the range ofbetween about 300 ppm to about 6000 ppm. Further, the catalyst system ofthe present invention is effective in treating organic phase containingnitrogen species such as quinolines and derivatives in amounts up toabout 1500 ppm.

The following examples further illustrate the catalyst system, processfor preparation and hydrogenation process of the present invention.

Unless indicated to the contrary, the hydrogenation processes of each ofthe following examples were carried out in a 300 ml autoclave, batchtype, with mechanical stirring at 630 rpm and temperature controlledheating unit with a total reaction volume of 100 ml. After six hours ofreaction for each process, the autoclave was allowed to cool to roomtemperature and was depresurized, and the organic phase was analyzed ina gas chromatography instrument, model Varian 3400. The reduction of thecontaminant concentration was measured in mol against an internalstandard using gas chromatography.

EXAMPLE 1

This example demonstrates the effectiveness of the catalyst system usingthree preparation methods in accordance with the present invention.

In accordance with a first method (method 1), ruthenium trichloridetrihydrate, sodium salt of TPPMS and aniline were added to water. For asecond method (method 2), aqueous solutions of the metal salt and TPPMSwere prepared, the aqueous metal solution was added to the TPPMSsolution, and the aniline was then added. For the third method (method3), aqueous solutions were prepared as in method 2, with the exceptionthat the TPPMS solution was added to the aqueous metal solution, andaniline was then added.

Six aqueous solutions were prepared using ruthenium trichloridetrihydrate (RuCl₃.3H₂ O) sodium salt of m-monosulfonated triphenylphosphine (TPPMS) and aniline as an organic nitrogen base.

Two solutions were prepared according to each of the methods 1, 2 and 3described above. The six aqueous solutions were tested for hydrogenatingtwo different contaminants, benzo[b]thiophene (BT) and quinoline (Qui),which were hydrogenated to their corresponding heteroaromatic rings as2,3-dihydrobenzo[b]thiophene (DHBT), 1,2,3,4-tetrahydroquinoline (THQ)and using decalin as the organic phase. The aqueous solution-organicphase mixture was formed in each case with a relation of water:decalineof 1:1, a total volume of 100 ml, and a relation of contaminant:catalystsystem of 50:1.

The process conditions were 1000 psi, 130° C., and 630 rpm, and theresults are shown in Table 1 where An=aniline.

                  TABLE 1                                                         ______________________________________                                                                                 %                                      Test Contamin Catalyst System Method Product Conv.                          ______________________________________                                        1    BT       RuCl.sub.3 + 6TPPMS + 6An                                                                    1     DHBT  18                                     2 BT RuCl.sub.3 + 6TPPMS + 6An 2 DHBT 22                                      3 BT RuCl.sub.3 + 6TPPMS + 6An 3 DHBT 80                                      4 Qui RuCl.sub.3 + 6TPPMS + 6An 1 THQ 76                                      5 Qui RuCl.sub.3 + 6TPPMS + 6An 2 THQ 95                                      6 Qui RuCl.sub.3 + 6TPPMS + 6An 3 THQ 100                                   ______________________________________                                    

As shown in Table 1, the catalyst system of the present inventionselectively hydrogenates the aromatic molecules at the heteroaromaticrings. Also, the best results are obtained for each contaminant usingmethod 3.

EXAMPLE 2

This example demonstrates activation of the catalyst system of thepresent invention using two different procedures. Two aqueous solutionswere prepared, each comprising a solution of ruthenium salt and asolution of water-soluble TPPMS ligand, prepared according to method 3of example 1 above, to which aniline was added as organic nitrogen base.The contaminant treated for in both solutions was benzo[b]thiophene (BT)in an organic phase of decaline. In test 1, the aqueous catalystsolution was introduced into the reactor under the following operatingconditions: pressure: 1000 psi, temperature: 130° C. and stirring of 630rpm, 6 hours reaction time. After one hour of activation, the organicphase was added to the reactor.

In test 2, the catalyst aqueous solution was introduced into the reactortogether with the organic phase solution containing contaminant, underthe same operation conditions of test 1. The reactor was closed andequilibrium of pressure and temperature was obtained after 45 minutes,at which time hydrogenation was commenced. The results are set forth inTable 2.

                                      TABLE 2                                     __________________________________________________________________________    Test.                                                                            contam-        water:De-                                                                          cont:cat                                                                           product                                             N° inant catalyst system calin ratio(mol) (s) % Conv.                __________________________________________________________________________    1  BT  RuCl.sub.3 + 6TPPMS + 6An                                                                1:1  50:1 DHBT                                                                              100                                             2 BT RUCl.sub.3 + 6TPPMS + 6An 1:1 50:1 DHBT 100                            __________________________________________________________________________

As shown, both procedures yield excellent results. However, Test 1proceeded at a higher rate than Test 2, which took two hours longer thanTest 1 to obtain the same conversion percentage. Thus, activation of theaqueous solution separately serves to speed up the hydrogenationreaction.

EXAMPLE 3

This example illustrates hydrogenation of aromatics containing sulfurand nitrogen atoms using different water-soluble ligands and differentGroup VIII metals in accordance with the invention.

Seventeen aqueous solutions were prepared and tested for thehydrogenation of the contaminants benzo[b]thiophene (BT) and quinoline(Qui). For each of the aqueous solutions, an aniline organic base wasused. The relation of water:decaline (organic phase) was 1:1, the ratioof contaminant:catalyst, in terms of mols, was 50:1. The processconditions were 1000 psi, 130° C. and 630 rpm. Table 3A shows theresults of tests 1 to 8 including conversion percentage with thecatalyst system using different water-soluble ligands. Table 3B showsthe results of Tests 9 to 17 using different Group VIII metals, TPPMS aswater-soluble ligand and aniline as organic nitrogen base.

                  TABLE 3A                                                        ______________________________________                                        Test                                 %                                          N° contaminant catalyst system product Conv.                         ______________________________________                                        1    Qui         RuCl.sub.3 + 6TPPMS                                                                         THQ   100                                        2 Qui RuCl.sub.3 + 6TPPTS THQ 67                                              3 Qui RuCl.sub.3 + 6biquiSO.sub.3 THQ 50                                      4 Qui RuCl.sub.3 + 6biquiCO.sub.2 THQ 42                                      5 BT RuCl.sub.3 + 6TPPMS DHBT 80                                              6 BT RuCl.sub.3 + 6TPPTS DHBT 38                                              7 BT RuCl.sub.3 + 6biquiCO.sub.2 DHBT 18                                      8 BT RuCl.sub.3 + 6biquiSO.sub.3 DHBT 22                                    ______________________________________                                    

                  TABLE 3B                                                        ______________________________________                                        Test                                   %                                        N° contaminant catalyst system product Conv.                         ______________________________________                                         9   BT         RuCl.sub.3 + TPPMS                                                                            DHBT   40                                       10 BT RuCl.sub.3 + TPPMS DHBT 42                                              11 BT RhCl.sub.3 + 6TPPMS+ DHBT 50                                            12 BT PdCl.sub.2 ((BCHD) + 6TPPMS DHBT 42                                     13 BT IrCl.sub.3 + 6TPPMS DHBT 33                                             14 Qui RuCl.sub.3 + TPPMS THQ 100*                                            15 Qui RhCl.sub.3 + 6TPPMS+ THQ 80                                            16 Qui PdCl.sub.2 ((BCHD) + 6TPPMS THQ 100*                                   17 Qui IrCl.sub.3 + 6TPPMS THQ 58                                           ______________________________________                                    

In tests 14 and 16, the hydrogenation of quinoline was very fast;quinoline was consumed even before the catalyst system obtained chemicalequilibrium. It can be seen from Tables 3A and 3B that the catalystsystem of the present invention is active for the hydrogenation of thecontaminants using a variety of ligands and metals.

EXAMPLE 4

This example illustrates the effect of the use of organic nitrogen base(ONB) as a co-catalyst with the catalyst system of the presentinvention. The organic nitrogen bases tested were: quinoline (Qui),aniline (An), isoquinoline (iQui), 1,2,3,4-tetrahydroquinoline (THQ),decahydroquinoline (DHQ), urea, acridine, piperidine and triethylamine(TEA). The tests were carried out under the following conditions:pressure, 1000 psi; temperature, 130° C.; ratio water:decalin, 1:1(v/v), for a time of 6 hours and stirring, 630 rpm. The catalyst systemformulation was: RuCl₃.3H₂ O+6(TPPMS)+6 ONB.

                                      TABLE 4                                     __________________________________________________________________________    Test                                                                             contami-           Cont:cat                                                  N° nant(s) catalyst system ONB ratio(mol) product(s) % Conv.         __________________________________________________________________________    1  BT   RuCl.sub.3 + 6TPPMS +                                                                  NO ONB                                                                             50:1 DHBT 42                                              2 BT RuCl.sub.3 + 6TPPMS + An 50:1 DHBT 100                                   3 BT RuCl.sub.3 + 6TPPMS + Qui 50:1 DHBT 100                                  4 BT RuCl.sub.3 + 6TPPMS + iQui 50:1 DHBT 100                                 5 BT RuCl.sub.3 + 6TPPMS + THQ 50:1 DHBT 88                                   6 BT RuCl.sub.3 + 6TPPMS + DHQ 50:1 DHBT 78                                   7 BT RuCl.sub.3 + 6TPPMS + acridine 50:1 DHBT 80                              8 BT RuCl.sub.3 + 6TPPMS + piperidine 50:1 DHBT 75                            9 BT RuCl.sub.3 + 6TPPMS + UREA 50:1 DHBT 75                                  10 BT RuCl.sub.3 + 6TPPMS + TEA 50:1 DHBT 63                                __________________________________________________________________________

From Table 4 it can be observed that the catalyst system of the presentinvention has a good activity without the organic nitrogen base, and aneven better activity when the organic base is added.

EXAMPLE 5

This example demonstrates the effect of the variation of concentrationof the organic nitrogen base. The concentration of the base isoquinoline[iQui] is in reference to the concentration of the metal, in mol,according to the expression: [ONB]:[RuCl₃.3H₂ O]. The conditions were:pressure, 500 psi H₂ ; temperature, 130° C.; stirring, 630 rpm; ratiowater/decalin: 1:1 (v/v). The molar ratio of contaminant:catalyst was25:1 for a time: 6 hrs.

                  TABLE 5                                                         ______________________________________                                        Test  contam-                [iQui]      %                                      N° inant(s) catalyst system (mol) product Conv.                      ______________________________________                                        1     BT      RuCl.sub.3 + 4TPPMS + iQui                                                                    0    DHBT  18                                     2 BT RuCl.sub.3 + 4TPPMS + iQui  1 DHBT 10                                    3 BT RuCl.sub.3 + 4TPPMS + iQui  3 DHBT 69                                    4 BT RuCl.sub.3 + 4TPPMS + iQui  5 DHBT 100*                                  5 BT RuCl.sub.3 + 4TPPMS + iQui 10 DHBT 100*                                  6 BT RuCl.sub.3 + 4TPPMS + iQui 15 DHBT 100*                                ______________________________________                                    

In tests 4 to 6 the hydrogenation process was so fast it was measured inminutes.

EXAMPLE 6

This example demonstrates the hydrogenation process as a function of theconcentration of Group VIII noble metal. The process conditions were:pressure, 500 psi H₂ ; temperature, 130° C.; stirring, 630 rpm; reactiontime, 3 hours. The metal concentration was taken in relation to theconcentration of the contaminant, both in mols. The catalyst system forthis example was: RuCl₃.3H₂ O, 4 BIQUIc(2,2'-biquinoline-5,5'-dicarboxylic acid dipotassium salt trihydrate), 5THQ (1,2,3,4-tetrahydroquinoline). Table 6 shows the results obtained.

                  TABLE 6                                                         ______________________________________                                        Test contam-               [RuCl.sub.3 ] %                                      N° inant(s) catalyst system (mol) product(s) Conv.                   ______________________________________                                        1    Qui      RuCl.sub.3 + 4BlQUlc +                                                                      1     THQ    20                                       5THQ                                                                        2 Qui RuCl.sub.3 + 4BlQUlc +  5 THQ 70                                          5THQ                                                                        3 Qui RuCl.sub.3 + 4BlQUlc +  8 THQ 66                                          5THQ                                                                        4 Qui RuCl.sub.3 + 4BlQUlc + 12 THQ 47                                          5THQ                                                                        5 Qui RuCl.sub.3 + 4BlQUlc + 25 THQ 38                                          5THQ                                                                        6 Qui RuCl.sub.3 + 4BlQUlc + 50 THQ 98                                          5THQ                                                                      ______________________________________                                    

EXAMPLE 7

This example illustrates the hydrogenation of heteroaromatic compounds(BT) as a function of the concentration of water soluble ligand (WSL).The example was carried out in a reactor of 75 ml for a total volume ofsolution of 50 ml, the stirring was provided using a magnetic bar. Theprocess conditions were 1000 psi and 130° C. during 4 hours of reaction.The results are set forth below in Table 7.

                                      TABLE 7                                     __________________________________________________________________________    Test                                                                             contami-        [WSL]                                                                             Cont:cat                                                 N° nant(s) catalyst system (mol) ratio(mol) product(s) %             __________________________________________________________________________                                     Conv.                                        1  BT   RuCl.sub.3 + TPPMS + 6Qui                                                                0   50:1 DHBT 18                                             2 BT RuCl.sub.3 + TPPMS + 6Qui 2 50:1 DHBT 23                                 3 BT RuCl.sub.3 + TPPMS + 6Qui 4 50:1 DHBT 53                                 4 BT RuCl.sub.3 + TPPMS + 6Qui 6 50:1 DHBT 65                                 5 BT RuCl.sub.3 + TPPMS + 6Qui 8 50:1 DHBT 67                                 6 BT RuCl.sub.3 + TPPMS + 6Qui 10 50:1 DHBT 46                              __________________________________________________________________________

The results showed that a molar concentration of WSL of between about 4to about 8, was most effective for the hydrogenation process.

EXAMPLE 8

Hydrogenation of heteroaromatics was carried out using the catalystsystem of the present invention and varying the amount of water inrelation to the amount of organic phase (decalin). The water variationdid not affect the total volume of solution of 100 ml, which wasmaintained by adding the quantity of organic phase required. Reactionconditions: time of reaction: 3 hours; pressure: 500 psi H₂ ;temperature: 130° C.; ratio water/decalin: variable (v/v); stirring: 630rpm; molar ratio of contaminant to decalin, 25:1. The results are setforth below in Table 8.

                                      TABLE 8                                     __________________________________________________________________________    Tests                                                                            contami-         [H.sub.2 O]                                                                       Cont:cat                                                N° nant(s) catalyst system (mL) ratio(mol) product(s) % Conv.        __________________________________________________________________________    1  BT   RuCl.sub.3 + 4TPPMS + 5iQui                                                               25  25:1 DHBT 50                                            2 BT RuCl.sub.3 + 4TPPMS + 5iQui 35 25:1 DHBT 61                              3 BT RuCl.sub.3 + 4TPPMS + 5iQui 50 25:1 DHBT 70                              4 BT RuCl.sub.3 + 4TPPMS + 5iQui 70 25:1 DHBT 84                            __________________________________________________________________________

EXAMPLE 9

Hydrogenation of heteroaromatic contaminant (BT) using the hydrosolublecatalyst system of the present invention is effected using as metalsource a soluble salt of the metal and also an organometallic compound.The hydrogenation of benzo[b]thiophene (BT) to2,3-dihydrobenzo[b]thiophene (DHBT) was carried out as shown in TABLE 9.The catalyst system had the following molar ratio: Ru source+6 TPPMS+6iQui. The reaction conditions: temperature, 130° C.; pressure, 500 psiH₂ ; stirring, 630 rpm, molar ratio of contaminant:catalyst system,50:1; volume of aqueous to organic phase, 1:1 (v/v) for a total volumeof 100 ml; reaction time, 6 hours.

                  TABLE 9                                                         ______________________________________                                        Expt.            catalyst system       %                                        N° contaminant(s) (Metal source) product(s) Conv.                    ______________________________________                                        1     BT         RuCl.sub.3.3H.sub.2 O                                                                        DHBT   100                                      2 BT RuBr.sub.3.nH.sub.2 O DHBT 67                                            3 BT RuI.sub.3.nH.sub.2 O DHBT 56                                             4 BT RuCl.sub.2 (MeCN).sub.4 DHBT 97                                          5 BT HRuCl(TPPMS).sub.2 (iQui).sub.2 DHBT 100                                 6 BT [RuHCl(TPPMS).sub.2 ].sub.2 DHBT 100                                   ______________________________________                                    

As shown in Table 9, the various metal sources provide excellentresults. Also, when metal is provided in organometallic form,water-soluble ligand and organic nitrogen base may already be present,as in tests 4 and 5, and addition of extra water-soluble ligand or ONBwas not necessary.

EXAMPLE 10

This example demonstrates the effect that the pressure has on thehydrogenation of heteroaromatic contaminants, using the catalyst systemof the present invention. For the hydrogenation process, the conditionswere: temperature, 130° C.; RuCl₃ was used in trihydrate form; organicmatrix, decaline; volume ratio water:decalin, 1:1 (v/v); total solutionvolume, 100 ml.

                                      TABLE 10                                    __________________________________________________________________________    Test.                PRESSURE                                                                             Cont:cat                                            N° contaminant catalyst system (PSI) ratio(mol) product %            __________________________________________________________________________                                          Conv.                                   1  BT     RuCl.sub.3 + 6TPPMS + 6An                                                                1000   50:1 DHBT 100                                       2 BT RuCl.sub.3 + 6TPPMS + 6An 500 50:1 DHBT  52                              3 BT RuCl.sub.3 + 6TPPMS + 6An 250 50:1 DHBT  37                              4 Qui RuCl.sub.3 + 6TPPMS + 6An 1000 50:1 THQ 100*                            5 Qui RuCl.sub.3 + 6TPPMS + 6An 500 50:1 THQ 100*                             6 Qui RuCl.sub.3 + 6TPPMS + 6An 300 50:1 THQ 100*                             7 Qui RuCl.sub.3 + 6IPPMS + 6An 250 50:1 THQ  80                              8 Qui RuCl.sub.3 + 6IPPMS + 6An 100 50:1 THQ  67                            __________________________________________________________________________

In tests 4, 5 and 6 the hydrogenation of quinoline was very rapid underthe given conditions. An analysis of the reaction profile, duringhydrogenation showed that the process was completed in minutes.

EXAMPLE 11

This example demonstrates the effect of temperature on hydrogenationusing the hydrosoluble catalyst system of the present invention. In thisexample, the reaction conditions were similar to those of in Example 10,with the exception that pressure was maintained at 500 psi and the molarratio of contaminant to catalyst system was 25:1. The results are shownin Table 11.

                                      TABLE 11                                    __________________________________________________________________________    Expt.                                                                            contami-               Cont:cat                                              N° nant(s) catalyst system Temp(° C.) ratio(mol) product(s                                        ) % Conv.                                 __________________________________________________________________________    1  BT   RuCl.sub.3 + 4TPPMS + 3                                                                   80    25:1 DHBT 56                                            iQui                                                                        2 BT RuCl.sub.3 + 4TPPMS + 3 100 25:1 DHBT 76                                   iQui                                                                        3 BT RuCl.sub.3 + 4TPPMS + 3iQui 120 25:1 DHBT 87                             4 BT RuCl.sub.3 + 4TPPMS + 3 130 25:1 DHBT 100                                  iQui                                                                        5 BT RUCl.sub.3 + 4TPPMS + 3 150 25:1 DHBT 68                                   iQui                                                                      __________________________________________________________________________

EXAMPLE 12

This example illustrates the selectivity of the catalyst system of thepresent invention. Seven tests were conducted for hydrogenation ofheteroaromatics in presence of other aromatic and olefinic compounds.The contaminants tested were: (BT) benzo[b]thiophene; (Qui) quinoline;(Th) thiophene; (Nap) Naphthalene; (CHD) 1,4-cyclohexadiene; (DCN)1-Decene; (COD) 1,5-cyclooctadiene and (Bz) benzene. Products obtainedwere: (DHBT) 2,3-dihydrobenzo[b]thiophene; (THQ)1,2,3,4-tetrahydroquinoline; (Nap)Naphthalene; (THTh)2,3,4,5-tetrahydrothiophene; (CHN) Cyclohexane; (COT) cyclooctane. Theresults are set forth in Table 12 below.

                                      TABLE 12                                    __________________________________________________________________________    Expt.                 Cont:cat ratio                                            N° contaminant(s) catalyst system (mol) product(s) % Conv.           __________________________________________________________________________    1  BT + Qui + Nap                                                                        RuCl.sub.3 + 6TPPMS + 6An                                                                50:1   DHBT + THQ + Nap                                                                        100:100:0                                2 BT + Th + Nap RuCl.sub.3 + 6TPPMS + 6An  5:1 DHBT + THTh + Nap                                                   100:60:0                                 3 BT + Th + Nap RuCl.sub.3 + 6TPPMS + 6An 50:1 DHBT + THTh + Nap                                                   100:9:0                                  4 BT + Qui + CHD RuCl.sub.3 + 6TPPMS + 6An 50:1 DHBT + THQ + CHN                                                   80:100:60                                5 BT + Qui + DCN RuCl.sub.3 + 6TPPMS + 6An 50:1 DHBT + THQ + DCN                                                   70:100:9                                 6 BT + Qui + COD RuCl.sub.3 + 6TPPMS + 6An 50:1 DHBT + THQ + COT                                                   90:100:17                                7 BT + Qui + Bz RuCl.sub.3 + 6TPPMS + 6An 50:1 DHBT + THQ + Bz              __________________________________________________________________________                                           98:100:0                           

As shown, the hydrosoluble catalyst system advantageously hydrogenatesaromatic compounds containing sulfur and nitrogen atoms without reducingother aromatics such as benzene, toluene and naphthalene. In thepresence of cyclic olefins or linear olefins the hydrogenation proceedsvery rapidly while reducing the olefins only in small percentages.

EXAMPLE 13

In this example, hydrogenation of heteroaromatic compounds were carriedout using different organic phases such as decaline(decahydronaphthaline), n-heptane, cyclohexene, n-octane, and naphthafrom coking and cracking processes. The naphtha used as organic phaseswere obtained from Venezuelan refineries: Naphtha from FCC process fromAmuay refinery with a sulfur content of 1,200 ppm (naphtha 1); a lightcokification naphtha from Cardon refinery with a sulfur content of 1,700ppm (naphtha 2); and a HDH(R) naphtha from a process for deephydroconversion of heavy oil with a sulfur content of 4,500 ppm (naphtha3). The process conditions were 1000 psi H2, temperature of 130° C., andstirring of 520 rpm; reaction time, 6 hrs. Results are shown in Table13.

                                      TABLE 13                                    __________________________________________________________________________    Test.                                                                            contami-        organic                                                                           Cont:cat                                                 N° nant(s) catalyst system matrix ratio(mol) product(s) %            __________________________________________________________________________                                       Conv.                                      1  BT + Qui                                                                           RuCl.sub.3 + TPPMS + 6An                                                                 decalin                                                                           50:1 DHBT + THQ                                                                           90:100                                       2 BT + Qui RuCl.sub.3 + TPPMS + 6An Heptane 50:1 DHBT + THQ 87:100                                              3 BT + Qui RuCl.sub.3 + TPPMS + 6An                                          naphtha 50:1 DHBT + THQ 66:100                                                    1                                        4 BT RuCl.sub.3 + TPPMS + 6Qui naphtha 5:1 DHBT 60                               2                                                                          5 BT RuCl.sub.3 + TPPMS + 6An naphtha 50:1 DHBT 67                               3                                                                          6 BT RuCl.sub.3 + TPPMS + 6An decane 50:1 DHBT 78                           __________________________________________________________________________

As shown, excellent results are obtained in accordance with inventionusing each organic phase.

This invention may be embodied in other forms or carried out in otherways without departing from the spirit or essential characteristicsthereof. The present embodiment is therefore to be considered as in allrespects illustrative and not restrictive, the scope of the inventionbeing indicated by the appended claims, and all changes which comewithin the meaning and range of equivalency are intended to be embracedtherein.

What is claimed is:
 1. A process for preparing a catalyst system forhydrogenation of sulfur-containing and nitrogen-containing compounds,comprising the steps of forming a first mixture of a noble metalselected from Group VIII of the Periodic Table of Elements in water anda second mixture of a sulfonated aryl phosphine water-soluble ligand inwater and thereafter mixing the first mixture and second mixturetogether so as to provide an aqueous catalyst system.
 2. A processaccording to claim 1, further comprising the step of adding an organicnitrogen base to the aqueous catalyst system.
 3. A process according toclaim 1, wherein the step of forming the aqueous catalyst systemcomprises adding the first mixture to the second mixture.
 4. A processaccording to claim 1, wherein the step of forming the mixture comprisesadding the second mixture to the first mixture.
 5. A process accordingto claim 1, wherein the forming step comprises providing a hydrogenationreactor and mixing the first and second mixtures in situ in saidhydrogenation reactor under hydrogenation conditions.
 6. A processaccording to claim 1, wherein the noble metal is selected from the groupconsisting of ruthenium, rhodium, palladium, iridium, platinum andmixtures thereof.
 7. A process according to claim 1, wherein the noblemetal is in the form of a noble metal compound selected from the groupconsisting of water soluble metal salts, organo metallic compounds andmixtures thereof.
 8. A process according to claim 1, wherein the noblemetal is in the form of a metal salt selected from the group consistingof chloride salt, bromide salt, iodide salt and mixtures thereof.
 9. Aprocess according to claim 1, wherein the noble metal is in the form ofan organometallic compound containing at least a portion of thewater-soluble ligand.
 10. A process according to claim 9, wherein theorganometallic compound is selected from the group consisting ofmetal-triacetylacetonate, metal-biacetylacetonate and mixture thereof.11. A process according to claim 1, wherein the water-soluble ligand isa sulfonated triaryl phosphine selected from the group consisting ofm-monosulfonated triphenyl phosphine, tri (m-sulfonated) triphenylphosphine and mixtures thereof.
 12. A process according to claim 11,wherein the sulfonated triaryl phosphine is in sodium salt form.
 13. Aprocess according to claim 1, wherein the water-soluble ligand is abiquinoline.
 14. A process according to claim 13, wherein thebiquinoline is selected from the group consisting of2,2'-biquinoline-4,4'-dicarboxylic acid in dipotassium salt form,trihydrate; 2,2'-biquinoline-5,5'-disulfonated in disodium salt form,dihydrate and mixtures thereof.
 15. A process according to claim 2wherein the organic nitrogen base is selected from the group consistingof aniline, quinoline, isoquinoline, tetrahydroquinoline,decahydroquinoline, acridine, piperidine, triethylamine and mixturesthereof so as to provide an aqueous catalyst system.